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ANALYTICAL CHEMISTRY
Chapter 1
Introduction
Analytical Chemistry deals with methods
for determining the chemical composition of
samples.
• Qualitative Analysis (identification)
provides information about the identity of
species or functional groups in the
sample (an analyte can be identified).
• Quantitative Analysis provides numerical
information of analyte (quantitate the
exact amount or concentration).
Analytical Methods
1. Spectroscopic methods:
a. Atomic spectroscopy
b. Molecular spectroscopy
2. Chromatographic methods
(separations):
3. Electrochemistry:
Block diagram of an instrumental measurement
Block diagram of a fluorometer
Applications of Instrumental
Methods
1. Bioanalytical: biological molecules and/or
biological matrices (e.g., proteins, amino
acids, blood, urine)
2. Environmental: pesticides, pollution, air,
water, soil
3. Material science: polymers,
characterization of new materials
4. Forensic science (application of science to
the law): body fluids, DNA, gun shot
residue, hair, fibers, elemental analysis,
drugs, alcohols, poisoning, fingerprints, etc.
Analytical Methodology
1. Plan: Qualitative or quantitative or both; what
kind of information have; which technique is
suitable etc.
2. Sampling: Accuracy depends on proper
sampling, characteristic of sample is very
important, required good representative
sample (from top, middle and bottom and mix
up and take average sample).
3. Sample preparation: depends on analytical
techniques.
4. Analytical measurement:
5. Data Analysis: Whether the data make sense
Selecting an Analytical Method
In order to select an analytical method intelligently, it is
essential to define clearly the nature of the analytical
problem. In general, the following points should be
considered when choosing an instrument for any
measurement.
1. Accuracy and precision required
2. Available sample amount
3. Concentration range of the analyte
4. Interference in sample
5. Physical and chemical properties of the sample matrix
6. Number of sample to be analyzed
7. Speed, ease, skill and cost of analysis
Figures of Merit
Precision
Bias
Sensitivity
Detection limit
Concentration range (Dynamic range)
Selectivity
Precision: How close the same measurements are
to one another. The degree of mutual agreement
among data that have been obtained in the same
way. Precision provides a measure of the random
or indeterminate error of an analysis.
Quartering Method
Mix samples thoroughly. Pour it onto a
large flat surface.
Divide the sample into four equal parts. Save Discard
Save the 2 opposite quarters. Be sure to
Discard Save
save the fine material at the bottom of the
saved quarter. If the sample is still to large,
divide the sample again.
Sampling
Sampling is the process of extracting from a large quantity of material a small portion,
which is truly representative of the composition of the whole material.
1) Three main group of sampling:
1> Census : all the material is examined impracticable
2> Casual sampling on an ad hoc basis unscientific
3> Statistical sampling
2) Sampling procedure
Bulk sample
homogeneous or heterogeneous
Increment
Gross sample
Sub sample
Analysis sample
Census vs Random sampling
Census
A complete enumeration, usually of a population, but also businesses and commercial
establishments, farms, governments, and so forth.
Random sampling
A commonly used sampling technique in which sample units are selected so that all
combinations of n units under consideration have an equal chance of being selected as
the sample.
(Statistical sampling meaning) A sampling method in which every possible sample has
the same chance of being selected.
3) Sampling statistics :
Total error = sampling error + analytical error
(2) Are you interested in all sample components or only one or a few?
If only a few then separation is necessary by extraction or
chromatography.
http://www.trincoll.edu/~dhenders/textfi~1/Chem%20208%20notes/sample_preparation.htm
Sampling particulate solids
Where:
N is the number of calibration data points.
L is the number of replicate measurements of the unknown.
and is the mean of the unknown measurements.
Chapter 2
Chemical Apparatus, and Unit Operation of
Analytical Chemistry
Classifying Chemicals
1. Reagent Grade: Reagent grade chemical conform to the minimum
standards set forth by the Reagent Chemical committee of the American
Chemical Society and are used wherever possible in analytical work.
2. Primary Standard Grade: Extraordinary purity is required for a primary
standard. Primary standard reagent is carefully analyzed and the assay is
printed on the container label.
3. Special-Purpose Reagent: chemicals that have been prepared for a
specific application. Included among these are solvents for
spectrophotometry and high-performance liquid chromatography.
3. Special-Purpose Reagent: chemicals that have been prepared for a
specific application. Included among these are solvents for
spectrophotometry and high-performance liquid chromatography.
2. Primary standard Grade: Extraordinary purity is required for a primary
standard. Primary standard reagent is carefully analyzed and the assay is
printed on the container label.
Rules for Handling Reagents and
Solutions
1. Select the best grade of chemical available for analytical
work.
2. Replace the top of every container immediately after
removal of the reagent.
3. Hold the stoppers of reagent bottles between your
fingers.
4. Never return any excess reagent to a bottle.
5. Never insert spatulas, spoons, or knives into a bottle
that contains a solid chemicals.
6. Keep the reagent shelf and the laboratory balance clean
and neat.
7. Observe regulations concerning the disposal of surplus
reagents and solutions.
Cleaning and Marking Laboratory Ware
Filtering Crucibles
Filtering crucibles serve not only as containers but also as
filters. A vacuum is used to hasten the filtration, a tight seal
between crucible and filtering flask is accomplished with any of
the several types of rubber adapters.
Filtering Crucible
Sintered-glass Crucibles
Sintered-glass crucibles are manufactured in fine, medium, and
coarse porosities. The upper temperature limit for sintered
glass crucible is ordinarily about 200oC. Filtering crucibles
made entirely of quartz can tolerate substantially higher
temperatures.
Filter Paper
Paper is an important filtering medium. Ashless paper is
manufactured from cellulose fibers that have been treated with
hydrochloric and hydrofluoric acids to remove metallic
impurities and silica, ammonia is then used to neutralize the
acids. It is necessary to destroy the paper by ignition if the
precipitate collected on it is to be weighed.
Decantation and transferring precipitate
Folding and seating a filter paper
Vacuum Filtration
Heating Equipment
Many precipitate can be weighed directly after being brought to
constant mass in a low temperature drying oven. Such an oven
is electrically heated and capable of maintaining a constant
temperature to within 1oC. The maximum attainable
temperature ranges from 140 to 260oC, depending on make
and model, for many precipitate 110oC is a satisfactory drying
temperature.
Microwave laboratory ovens are currently appearing on the
market. Where applicable, these greatly shorten drying cycles.
Muffle furnace (a heavy duty electric furnace) is capable of
maintaining controlled temperatures of 1100oC or higher. Long
handled tongs and heat resistance gloves are needed for
protection.
Volume Measurement
Pipets
Burets
Volumetric flask
Measuring cylinder
Typical pipets
Automatic pipet
Burets and volumetric flask
Reading a buret
Using pipet
Titration
Calibrating Glassware
• (left) Carbon-fiber electrode with a 100-nanometer-diameter (100 × 10−9 meter) tip extending from glass capillary.
The marker bar is 200 micrometers (200 × 10−6 meter). [From W.-H. Huang, D.-W. Pang, H. Tong, Z.-L. Wang,
and J.-K. Cheng, Anal. Chem. 2001, 73, 1048.] (middle) Electrode positioned adjacent to a cell detects release of
the neurotransmitter, dopamine, from the cell. A nearby, larger counterelectrode is not shown. (right) Bursts of
electric current detected when dopamine is released. Insets are enlargements. [From W.-Z. Wu, W.-H. Huang, W.
Wang, Z.-L. Wang, J.-K. Cheng, T. Xu, R.-Y. Zhang, Y. Chen, and J. Liu, J. Am. Chem. Soc. 2005, 127, 8914.]
Chapter 1: Measurements
1-1 SI Units
Using prefixes as multipliers
We customarily use prefixes for every third power of ten, e.g. 10-9.
10-6, 10-3 …
Converting between units
Example: Express the energy 20 Calories in terms of ? kilojoules (kJ)
Why should we be concerned of units?
• Dilution
Solution:
STATISTICAL TESTS
AND ERROR
ANALYSIS
PRECISION AND ACCURACY
PRECISION – Reproducibility of the result
ACCURACY – Nearness to the “true” value
TESTING ACCURACY
TESTING PRECISION
SYSTEMATIC / DETERMINATE ERROR
• Reproducible under the same conditions in the same
experiment
• Can be detected and corrected for
• It is always positive or always negative
Characterised by:
The standard
deviation – s
measures the width of
the distribution
The mean or average, x
the sum of the measured values (xi) divided by the
number of measurements (n)
n
_ xi
i1
x
n
The standard deviation, s
measures how closely the data are clustered about
the mean (i.e. the precision of the data)
2
x i x
i
s
n1
• Variance
Variance = s2
NB DON’T round a
std dev. calc until
the very end.
The first decimal place
of the standard
x 754
754 4 ppb Pb deviation is the last
s 3.77 significant figure of the
average or mean.
Also:
s 3.77
RSD 0.00500
x 754
s 3.77
% RSD 100 100 0.500%
x 754
μx
_ ts
μ 1.63
0.765 0.131
n 4
μ 1.63 0.05
There is a 50% chance that the true
mean lies between 1.58 and 1.68
ppm
x = 1.63
s = 0.131
1.78
90% confidence:
90%
t = 2.353 for n-1 = 3
1.68
_ ts
μ x 1.63
n 50%
1.58
μ 1.63
2.3530.131
4
μ 1.63 0.15 1.48
known value x
t calc n
s
tcalc > ttable at 95% confidence level
results are considered to be different
the difference is significant!
d
t calc n d = the average difference between
sd methods A and B
n = number of pairs of data
Where
sd (di d )2
n1
(di)
sd
0.022 0.222 0.112 0.112 0.022 0.04 2
61
sd 0.12
d
t calc n
sd
ttable = 2.571 for 95%
t calc
0.06
6 confidence
0.12
tcalc < ttable
t calc 1.2
difference between results
is NOT significant.
F TEST
COMPARISON OF TWO STANDARD
DEVIATIONS
s12
Fcalc
s2 2
Gap
Q = Range
Analytical Figures of Merit
“Indicate a characteristic of an instrumental
technique for a given analyte”
“7”
Accuracy, Precision, Signal-to-Noise Ratio
Sensitivity, Limit of Detection
Linearity, Linear Dynamic Range
Accuracy
Indicates how close the measured value is
to the true analytical concentration
│Cm - Ct│
x 100%
Ct
where:
Cm = measured concentration
Ct = true concentration
Precision
Indicates the reproducibility of repetitive
measurements of equivalent samples
1. Standard Deviation (s or σ)
2. Relative Standard Deviation (RSD)
3. Confidence Limits
Precision
Standard Deviation
For an infinite number of measurements (σ)
Rule of thumb: 16
45
35
30
Population
25
20
15
10
0
96.0 97.0 98.0 99.0 100.0 101.0 102.0 103.0 104.0
Value
1.00%
0.90% How far is the measured mean from the true value?
0.80%
0.70%
Error in Mean
0.60%
0.50%
0.40%
0.30%
0.20%
0.10%
0.00%
0 5 10 15 20 25 30 35 40 45 50
Number of Samples
70.0%
60.0%
How far is s from σ?
50.0%
Error in Std. Dev.
40.0%
30.0%
20.0%
10.0%
0.0%
0 5 10 15 20 25 30 35 40 45 50
Number of Samples
Short Cut: σ ≈ 1/5 (peak-to-peak noise)
Relative Standard Deviation
RSD = σ/mean
Notes:
1. N = noise (σ)
2. S/N is unitless
3. Always try top maximize S/N
4. S/N is used to compare instruments
5. A plot of S/N versus an instrumental parameter reaches
a maximum at the optimum value for that parameter
Sensitivity
Experimental slope of a calibration curve
m = ΔS/ΔC
90
80
70
60
Signal (V)
50 m
40
30 LOD
20
10
LDR
0
0 2 4 6 8 10 12
Concentration (ppm)
Limit of Detection
The analyte concentration yielding an
analytical signal equal to 3 times the
standard deviation in the blank signal.
LOD = 3 x σbl / m
SA = mC
SA = Analytical Signal
m = calibration sensitivity
Upper End
Analyte Concentration where the observed
signal falls 5% below the extrapolated line
LDR Units are
“orders of magnitude”
or
“decades”
of analyte concentration
Data Handling
141
Accuracy and Precision
Accuracy can be defined as the degree of
agreement between a measured value and
the true or accepted value. As the two values
become closer, the measured value is said to
be more accurate.
142
Assuming the correct or accepted value is
represented by the center of the circles
below, if all values occurred within, for
example, the red circles, results are
precise but not accurate. If all values
occurred within the yellow circle, results
are both accurate and precise. If results
were scattered randomly, results are
neither precise nor accurate.
143
144
Example
146
Some information about
measurements
1) Examples we will study include the metric ruler,
the graduated cylinder, and the scale.
2) Because of the involvement of human beings,
NO measurement is exact; some error is always
involved. This means that every answer in
science has some uncertainty associated with it.
We might be fairly confident we have the correct
answer, but we can never be 100% certain we
have the EXACT correct answer.
147
3) Measurements always have two parts - a
numerical part (sometimes called a factor) and a
dimension (a unit). The reason for this is that we
are measuring quantities - length, elapsed time,
temperature, mass, etc. Not only do we have to
tell how much there is, but we have to tell how
much of what.
Measuring gives significance (or meaning) to each
digit in the number produced. This concept of
significance, of what is and what is not
significant is VERY IMPORTANT.
148
The concept of significant figures (or
significant digits) is important. A
measurement can be defined as the
comparison of the dimensions of an object
to some standard.
The dimensions of an object refer to some
property the object possesses. Examples
include mass, length, area, density, and
electrical charge. Dimensions are often
called units.
149
Identifying significant digits
150
4. Zeroes between nonzero digits are significant.
e.g., 40.1m has 3 sig figs
5. Zeroes at the end of a number that contains a
decimal point are significant.
e.g., 41.0m has 3 sig figs, while 441.20m has 5.
In scientific notation, these can be written
respectively as
4.10*101 and 4.4120*102
6. Zeroes at the end of a number that does not
contain a decimal point may or may not be
significant. If we wish to indicate the number of
significant figures in such numbers, it is common
to use the scientific notation.
151
e.g., The quantity 52800 km could be having 3, 4,
or 5 sig figs—the information is insufficient for
decision. If both of the zeroes are used just to
position the decimal point (i.e., the number was
measured with estimation ±100), the number is
5.28×104 km (3 sig figs) in scientific notation. If
only one of the zeroes is used to position the
decimal point (i.e., the number was measured
±10), the number is 5.280×104 km (4 sig figs). If
the number is 52800±1 km , it implies
5.2800×104 km (5 sig figs).
152
Exact Numbers
Exact numbers can be considered as having an unlimited
number of significant figures. This applies to defined
quantities too. e.g.,
154
The general rule for estimation of the last
digit is to record to 1/10th of the smallest
division of the measuring device. So, for
the common centimeter-ruler, in which the
smallest division is 1mm, the estimate for
the last digit can be to 0.1mm which is
1/10th, of the smallest division.
155
Suppose a student records a length of
26.2mm with a ruler (between the red
marks). In his/her judgment, the length is
greater than 26.1mm but less than
26.3mm, and so the best estimate is
26.2mm. The measurement can be written
as 26.2±0.1 mm. The number 26.2mm
contains three significant figures. Although
the last digit, 2, is an estimate, it is
considered to be a significant figure for the
measurement.
156
How do you read it?
157
158
159
160
161
Math With Significant Figures
Addition and Subtraction
In mathematical operations involving significant figures, the
answer is reported in such a way that it reflects the
reliability of the least precise operation. Let's state that
another way: a chain is no stronger than its weakest link.
An answer is no more precise that the least precise
number used to get the answer. Let's do it one more
time: imagine a team race where you and your team
must finish together. Who dictates the speed of the
team? Of course, the slowest member of the team. Your
answer cannot be MORE precise than the least precise
measurement.
162
For addition and subtraction, look at the decimal
portion (i.e., to the right of the decimal point) of
the numbers ONLY. Here is what to do:
1) Count the number of significant figures in the
decimal portion of each number in the problem.
(The digits to the left of the decimal place are not
used to determine the number of decimal places
in the final answer.)
2) Add or subtract in the normal fashion.
3) Round the answer to the LEAST number of
places in the decimal portion of any number in
the problem.
163
Find the formula weight for Ag2MoO4 given the
following atomic weights: Ag = 107.870, Mo =
95.94, O = 15.9994.
The number with the least number of digits after
the decimal point is 95.94 which has two digits
for expression of precision. Also, it is the number
with the highest uncertainty. The atomic weights
for Ag and O have 3 and 4 digits after the
decimal point. Therefore if we calculate the
formula weight we will get 375.6776. However,
the answer should be reported as 375.68 ( i.e. to
the same uncertainty of the least precise value.
164
Multiplication and Division
In mathematical operations involving significant
figures, the answer is reported in such a way
that it reflects the reliability of the least precise
operation. Let's state that another way: a chain
is no stronger than its weakest link. An answer is
no more precise that the least precise number
used to get the answer. Let's do it one more
time: imagine a team race where you and your
team must finish together. Who dictates the
speed of the team? Of course, the slowest
member of the team. Your answer cannot be
MORE precise than the least precise
measurement.
165
The following rule applies for multiplication and
division:
The number having the least number of significant
figures is called the KEY NUMBER. The LEAST
number of significant figures in any number of
the problem determines the number of
significant figures in the answer.
This means you MUST know how to recognize
significant figures in order to use this rule.
In case where two or more numbers have the
same least number of significant figures, the key
number is determined as the number of the
lowest value regardless of decimal point.
166
2.5 x 3.42.
The answer to this problem would be 8.6
(which was rounded from the calculator
reading of 8.55). Why?
168
Example
Synthetic Chemistry Analytical Chemistry
“white powder”
Qualitative Quantitative
to identify to analyze
This white powder is to determine X in a sample
to quantify
NaCl
to measure
0.375 mg/mL caffeine
to detect
There is a trace Run assay
admixture determination
of iodine in this quantitation
sample Composition, %%:
Cu, 85.34(3); Zn, 11.23; Sn, 1.02(2);
Fe, 0.123(2); Mn, 0.058(5); Ni, 0.229(5); …
An example from Harris: